Nitro derivative of anilin and process for the manufacture of same.



UNITED STATES PATENT orrrou IBERNHA RD JACQUES FLI IBSCHEIM, 0F FLEET, ENGLAND.

NITRO DERIVATIVE OF ANILIN AND PROCESS FOR THE MANUFACTURE SAME.

No Drawing.

To all whom it may concern:

Be it known that I, BERNHARD JACQUES Fm'msonnmr, doctor of philosophy and research chemist, by birth a German subject, but having applied for naturalization as a British subject, and, a resident of Fleet, Hampshire, England, have invented a new and useful Nitro Derivative of Anilin and Process for the Manufacture of Same, of which the following is a specification.

Among the derivatives of anilin, which are unsubstituted in the amino group, trinitro-anilin has hitherto been the richest in nitro groups. y

I have discovered, that a tetra-nitro-anilin may be obtained, if one of the following compounds, or a mixture of two or more of them is treated with sulfuric acid and a nitrating agent, with or without the addition of other suitable materials: 1. Meta-nitroanilin (crude or pure). 2. A compound derivable from meta-nitro-anilin by the substitution for hydrogen attached to the aminonitrogen of one or more suitable acid radicals, such as CO.Alkyl, -CO.Ary1, S0,.Ary1

or in ortho or para position to the same, such as SO,H,COOH, or in several of these positions, or by combining the amino nitrogen with an aldehydic radical, when again one or more suitable acid radicals may be in the ortho or para positions with regard to the aldehyde-substituted amino,

diacetyl-meta nitro-anilid, ben z oyl metanitro-anilid, ortho-amino-para-nitrobenzoic Specification of Letters Eatent.

isolated by filtration;

Patented Nov. 19, 1912.

Application filed February 4, 1911. Serial No. 606,588.

acid, 3-nitro-4-sulfanilic acid, O-acetaminopara-nitrobenzoic acid, m-nitro-benzylidenemeta nitro-anilin, meta nitro-benzylidene- 3A-dinitro-anilin, etc.

Examples for (3) are a solution of 3.45- dinitro-acet-anilid in sulfuric acid, as it is obtained by the nitration of m-nitro-acetanilid; a solution of ni-nitro-aniline in sulfuric acid, as it is obtained by the nitration of anilin; a solution of a mixture of 2.3-dinitroacetanilid with 3.4- and 3.6-dinitro-acetanilids, as it is obtained by the nitration of meta-nitro-acetanilid in a mixture of nitric V and sulfuric acids, etc.

The sulfuric acid used may according, to the nature of the aromatic compound employed either only be fairly concentrated (for instance 60 B.), or concentrated (for instance 66 1%.), or monohydrated, or fuming. The nitrating agent may be nitric acid, or its salts, or its ethers or its anhydrids (for instance sodium nitrate 0r acetylnitrate or ethyl-nitrate). The temperature of the reaction, the proportions of the ingredients, the mode of mixing them, the

temperature at which they are mixed, and the mode of isolating the tetra-nitrO-anilin,

may be varied within wide limits;

The sulfuric acid may be used once only, or it may be used repeatedly, for nitrating new quantities of the above compounds; it is finally still suitable for many industrial purposes, such as the manufacture of nitric acid from nitrate.

Example I rl part of meta-nitro-anilin and 2% parts-9f so ium nitrate are dissolved in about 36 to 40 parts of concentrated sulfuric acid; the mass is then heated to about" 70 C. to C. and if necessary external cooling is applied, to prevent the temperature from rising above C. When the react-ion has subsided, the mass is heated further, to 100 C. for a few. minutes, then allowed to cool, and the tetra-nitro-anilin Example II: One part of meta-nitro-anilin is dissolved in 36 parts of strong sulfuric acid (eitherconcentratedacid or mono- Phydrate or fuming acid), 21} parts of sodium-nitrate are-then added, and the mass is allowed to remain at the ordinary temperature or at a lower or only slightly higher temperature for several days.

lflxam'ple Ill: One part of meta-nitroacctauilid tll.-.\'()l\'(tl in 20 parts of strong sulfuric acid with 2 parts of sodiuni-nitrate (or an approximately eimivaleul amount of strong nitric acid} and either allowed to r main for some day at ordinar temperature. or it is heated. l' r instan to 100 (l. The same sulfuric acid may be u ed again, as under I l.

Example lV: :Ll tlil1ll'l01llilllll or 3.4- dinitro-acetanilid treated as under II].

Example V: flihtlinilro-aniliu or Bil-dinitroacetani!id is treaic-il as under .llI.

Example VI: Ortho amino para nitrobenzoic acid ooon sin or meta-iiitro-parasulphanilic acid l /nao,

5 N flg are converted into tetra -nitro anilin by treating 1 part ot' any of these with two parts of soditun-nitrate in 90 parts of concentrated sulfuric acid, at 50 to 100 C.

Example VII: A solution at PEA-dinitroacctanilid. obtained for instance by treating 1. part of m-nitro-acetanilid with 1.15 parts of dry potassilnn-nitrate in 153 parts of sult'uric acid monohyalrale. at. the ordinary temperature for it hours is, after adding another '1 parts of potassium -nitrate, heatcdto 100 C Example VlIl: 1 part of m-nitrmanilin. 9.5 partsot sodium-nitrate, and parts of concentrated sulfuric acid are heated slowly. to (35. The temperature is then allowed to rise. without external heating" or cooliruz'. cool ing.

Example TX. 20 parts of cone. sulfuric ac d (or monohydrate or fuming acid) are heated to 1 part of m-nitro-aniiiu and parts of sodium-nitrate may then be idded gradually in different way they may for instance. be mixed and then added; or the whole of the nitrate may first be added. and the nitro-anilin gradually atteiwvard, or he nitro-anilin may be dissolved first and .he nitrate gradually added; or both compounds may be alternately added in portions.

The precipitate is filtered after Example X: 1 part of m-nitro-anilin, 1.3 parts of m-nitro-acet-anilid, 5 parts of sodium-nitrate, and 56 parts of sulfuric acid are gradually heated to 100 C.

Example XI: 1 part of In nit-r0 bcnzyli- (lcnc m nitroanilin, together with 1.25 parts of smliamnitrate and 20 parts of 'suluric acid are gradually heated to 100 C.

The tetra -nitro-anilin obtained as described. is a yellow crystalline product or powder having a specific gravity of about and melting at about 210212 C. with deeompositimi. It is easily soluble in acetone, le luble in acetic acid, benzene and chloroform and almost insoluble in cold water. it can be re-crystallized, for instance tron) guacial acetic acid, or from nitro-benzeue or xylene and is characterized by the remarkable facility with which its nitro group in the 3 position may be replaced by other groups. Thus the compound can in ruretonc solution, for instance, be quantitatively transformed into tri-nitrometa-amino-phenol melting at 174 to 175 C.. by treatment with a--. aqueous solution of sodium acetate at ordinary temperature. The nitro group in the 3-position can also be replaced by numerous other radicals, for instance by amins; the amino group can equally be replaced, though not so easily.

The chemical constitution may be indi cated by the formula:

/ noi The new nitro compound may be used in the manufacture of explosives and dyes.

lVhat- I claim is 1. The" rocess for manufacture of tetranitro-ani in, which consists in treating :1 meta nitro derivative of an aromatic amino compound with sulfuric acid and a nitrat' i111 agent, substantially as described.

2. The process for the manufacture of a tetra-nitro-anilin, which consists in treating meta-nitro-anilin with sulfuric acid and a nitrating agent, substantially as described.

3. its a new product, tetra nitro -ani]in, being a yellow crystalline compound or a powder of the constitution /NOz l and about 1.8 specific gravity, melting at In testimony whereof I have signed my name to this specification in the presence of two subscribing witnesses.

BERNHARD JACQUES FLllRSCHEIM.

\Vitnesses J. \VETTER,

H. D. Jameson.

Copies of this patent may be obtained for five cents each, by addressing the Commissioner of ratents.

- Washington, D. C.

about 210. C. with decomposition, almost insoluble in cold Water, easily soluble in acetone, less soluble in acetic acid, benzene and Xylene, re-crystallizable from nitro-benzene, and distinguished by the facility, with which its nitro group in the 3-position may be replaced by other groups. 

